Hybrid Iron(II) Phthalocyaninoclathrochelates with a Terminal Reactive Vinyl Group and Their Organo-Inorganic Polymeric Derivatives: Synthetic Approaches, X-ray Structures and Copolymerization with Styrene | Sciact - CRIS-system of Boreskov Institute of Catalysis

Hybrid Iron(II) Phthalocyaninoclathrochelates with a Terminal Reactive Vinyl Group and Their Organo-Inorganic Polymeric Derivatives: Synthetic Approaches, X-ray Structures and Copolymerization with Styrene Full article

Journal

Dalton Transactions
ISSN: 1477-9226 , E-ISSN: 1477-9234

Output data

Year: 2022, Volume: 51, Number: 14, Pages: 5645-5659 Pages count : 15 DOI: 10.1039/d1dt04187h

Tags

Copolymerization; Fourier transform infrared spectroscopy; Ion exchange; Iron compounds; Molar ratio; Single crystals; Zirconium compounds

Authors

Dudkin Semyon V. ¹ , Chuprin Alexander S. ¹ , Belova Svetlana A. ¹ , Vologzhanina Anna V. ¹ , Zubavichus Yan V. ² , Kaletina Polina M. ³ , Shundrina Inna K. ³ , Bagryanskaya Elena G. ³ , Voloshin Yan Z. ^1,4

Affiliations

1	Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences, 28 Vavilova st., 119991 Moscow, Russia
2	Synchrotron Radiation Facility SKIF, Boreskov Institute of Catalysis of the Siberian Branch of the Russian Academy of Sciences, 1 Nikolskii pr., 6305590 Koltsovo, Russia
3	Vorozhtsov Novosibirsk Institute of Organic Chemistry Siberian Branch of Russian Academy of Sciences, 9 Lavrentiev pr., 630090 Novosibirsk, Russia
4	Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences, 31 Leninsky pr., 119991 Moscow, Russia

Funding (5)

1	Russian Science Foundation	22-23-00765 (122012700324-2)
2	Ministry of Science and Higher Education of the Russian Federation
3	Ministry of Science and Higher Education of the Russian Federation	ГЗ-2021-2023
4	Ministry of Science and Higher Education of the Russian Federation	14.W03.31.0034
5	Ministry of Science and Higher Education of the Russian Federation	0238-2021-0006 (АААА-А21-121011490013-7)

First hybrid metallo(IV)phthalocyaninate-capped tris-dioximate iron(II) complexes (so-called “phthalocyaninatoclatrochelates”) with non-equivalent apical fragments, functionalized with one terminal reactive vinyl group, were prepared using three different synthetic approaches: (i) by a transmetallation (capping group exchange) of the appropriate labile boron, antimony-capped cage precursors, (ii) via a capping of the initially isolated reactive semiclathrochelate intermediate, and (iii) using the direct one-pot template condensation of their ligand synthons on the iron(II) ion as a matrix. Thus obtained polytopic cage complexes were characterized using elemental analysis, 1H NMR, MALDI-TOF MS, and UV–vis spectra, and by the single crystal X-ray diffraction experiments. One of the obtained vinyl-terminated iron(II) phthalocyaninatoclathrochelates and its semiclatrochelate precursor were tested as olefin monomers in their copolymerization reaction with styrene as a main component. These vinyl-terminated (semi)clathrochelate iron(II) complexes were found to be successfully copolymerized with this industrially important monomer, thus giving the intensively colored copolymer products. Because of a low solubility of the tested zirconium(IV) phthalocyaninate-capped tris-nioximate monomer in styrene as a solvent, their molar ratio of 1:500 was used. Thus obtained copolymer products and the kinetic of their formation were studied using GPC, FTIR, UV-vis, TGA and DSC methods. Even at such a low concentration of this Fe,Zr-binuclear metallocomplex component, an increase as in the rate of UV-light degradation of these organo-inorganic products, as in their thermal stability, is found.

Dudkin S.V. , Chuprin A.S. , Belova S.A. , Vologzhanina A.V. , Zubavichus Y.V. , Kaletina P.M. , Shundrina I.K. , Bagryanskaya E.G. , Voloshin Y.Z.
Hybrid Iron(II) Phthalocyaninoclathrochelates with a Terminal Reactive Vinyl Group and Their Organo-Inorganic Polymeric Derivatives: Synthetic Approaches, X-ray Structures and Copolymerization with Styrene
Dalton Transactions. 2022. V.51. N14. P.5645-5659. DOI: 10.1039/d1dt04187h WOS Scopus РИНЦ ANCAN PMID OpenAlex publication_identifier_short.sciact_skif_identifier_type

Submitted:	Dec 13, 2021
Accepted:	Mar 9, 2022
Published online:	Mar 9, 2022
Published print:	Apr 14, 2022

Web of science:	WOS:000772519600001
Scopus:	2-s2.0-85127869380
Elibrary:	48425882
Chemical Abstracts:	2022:790348
Chemical Abstracts (print):	178:253996
PMID:	35322826
OpenAlex:	W4220896790
publication_identifier.sciact_skif_identifier_type:	520

DB	Citing
Web of science	9
Scopus	9
OpenAlex	8